Selective suppression of dry-etch rate of materials containing both silicon and oxygen

ABSTRACT

A method of suppressing the etch rate for exposed silicon-and-oxygen-containing material on patterned heterogeneous structures is described and includes a two stage remote plasma etch. Examples of materials whose selectivity is increased using this technique include silicon nitride and silicon. The first stage of the remote plasma etch reacts plasma effluents with the patterned heterogeneous structures to form protective solid by-product on the silicon-and-oxygen-containing material. The plasma effluents of the first stage are formed from a remote plasma of a combination of precursors, including a nitrogen-containing precursor and a hydrogen-containing precursor. The second stage of the remote plasma etch also reacts plasma effluents with the patterned heterogeneous structures to selectively remove material which lacks the protective solid by-product. The plasma effluents of the second stage are formed from a remote plasma of a fluorine-containing precursor.

CROSS-REFERENCES TO RELATED APPLICATIONS

This application claims the benefit of U.S. Prov Pat. App. No.61/527,823 filed Aug. 26, 2011, and titled “SELECTIVE SUPPRESSION OFDRY-ETCH RATE OF MATERIALS CONTAINING BOTH SILICON AND OXYGEN,” which isentirely incorporated herein by reference for all purposes.

BACKGROUND OF THE INVENTION

Integrated circuits are made possible by processes which produceintricately patterned material layers on substrate surfaces. Producingpatterned material on a substrate requires controlled methods forremoval of exposed material. Chemical etching is used for a variety ofpurposes including transferring a pattern in photoresist into underlyinglayers, thinning layers or thinning lateral dimensions of featuresalready present on the surface. Often it is desirable to have an etchprocess which etches one material faster than another helping e.g. apattern transfer process proceed. Such an etch process is said to beselective to the first material. As a result of the diversity ofmaterials, circuits and processes, etch processes have been developedwith a selectivity towards a variety of materials. However, there arefew options for selectively etching silicon faster than silicon oxide.

Dry etch processes are often desirable for selectively removing materialfrom semiconductor substrates. The desirability stems from the abilityto gently remove material from miniature structures with minimalphysical disturbance. Dry etch processes also allow the etch rate to beabruptly stopped by removing the gas phase reagents. Some dry-etchprocesses involve the exposure of a substrate to remote plasmaby-products formed from one or more precursors. For example, remoteplasma excitation of ammonia and nitrogen trifluoride enables siliconoxide to be selectively removed from a patterned substrate when theplasma effluents are flowed into the substrate processing region.Recently, dry etch processes have been developed which can removesilicon faster than silicon oxide, however, some applications mayrequire enhanced selectivities.

Methods are needed to improve silicon selectively relatively to siliconoxide and other silicon and oxygen containing materials using dry etchprocesses.

BRIEF SUMMARY OF THE INVENTION

A method of suppressing the etch rate for exposedsilicon-and-oxygen-containing material on patterned heterogeneousstructures is described and includes a two stage remote plasma etch.Examples of materials whose selectivity is increased using thistechnique include silicon nitride and silicon. The first stage of theremote plasma etch reacts plasma effluents with the patternedheterogeneous structures to form protective solid by-product on thesilicon-and-oxygen-containing material. The plasma effluents of thefirst stage are formed from a remote plasma of a combination ofprecursors, including a nitrogen-containing precursor and ahydrogen-containing precursor. The second stage of the remote plasmaetch also reacts plasma effluents with the patterned heterogeneousstructures to selectively remove material which lacks the protectivesolid by-product. The plasma effluents of the second stage are formedfrom a remote plasma of a fluorine-containing precursor.

Embodiments of the invention include methods of etching a patternedsubstrate in a substrate processing region of a substrate processingchamber, The patterned substrate has an exposedsilicon-and-oxygen-containing region and an exposed region of a secondmaterial having a different chemical stoichiometry from theexposed-silicon-and-oxygen-containing region. The method comprisessequential steps of: (1) a first dry etch stage comprising flowing eachof a first fluorine-containing precursor and a hydrogen-containingprecursor into a remote plasma region fluidly coupled to the substrateprocessing region while forming a first plasma in the plasma region toproduce first plasma effluents, and forming protective solid by-producton the exposed silicon-and-oxygen-containing region to form a protectedsilicon-and-oxygen-containing region; (2) a second dry etch stagecomprising flowing a second fluorine-containing precursor into theremote plasma region while forming a second plasma in the plasma regionto produce second plasma effluents, and etching the exposed region ofthe second material faster than the protectedsilicon-and-oxygen-containing region by flowing the plasma effluentsinto the substrate processing region through through-holes in ashowerhead; and (3) sublimating the protective solid by-product from theprotected silicon-and-oxygen-containing region by raising a temperatureof the patterned substrate. Forming the protective solid by-productincludes flowing the first plasma effluents into the substrateprocessing region in the showerhead.

Additional embodiments and features are set forth in part in thedescription that follows, and in part will become apparent to thoseskilled in the art upon examination of the specification or may belearned by the practice of the disclosed embodiments. The features andadvantages of the disclosed embodiments may be realized and attained bymeans of the instrumentalities, combinations, and methods described inthe specification.

BRIEF DESCRIPTION OF THE DRAWINGS

A further understanding of the nature and advantages of the disclosedembodiments may be realized by reference to the remaining portions ofthe specification and the drawings.

FIG. 1 is a flow chart of a dry etch process, having a selectivelysuppressed silicon oxide etch rate, according to disclosed embodiments.

FIG. 2A shows a substrate processing chamber according to embodiments ofthe invention.

FIG. 2B shows a showerhead of a substrate processing chamber accordingto embodiments of the invention.

FIG. 3 shows a substrate processing system according to embodiments ofthe invention.

In the appended figures, similar components and/or features may have thesame reference label. Further, various components of the same type maybe distinguished by following the reference label by a dash and a secondlabel that distinguishes among the similar components. If only the firstreference label is used in the specification, the description isapplicable to any one of the similar components having the same firstreference label irrespective of the second reference label.

DETAILED DESCRIPTION OF THE INVENTION

A method of suppressing the etch rate for exposedsilicon-and-oxygen-containing material on patterned heterogeneousstructures is described and includes a two stage remote plasma etch.Examples of materials whose selectivity is increased using thistechnique include silicon nitride and silicon. The first stage of theremote plasma etch reacts plasma effluents with the patternedheterogeneous structures to form protective solid by-product on thesilicon-and-oxygen-containing material. The plasma effluents of thefirst stage are formed from a remote plasma of a combination ofprecursors, including a nitrogen-containing precursor and ahydrogen-containing precursor. The second stage of the remote plasmaetch also reacts plasma effluents with the patterned heterogeneousstructures to selectively remove material which lacks the protectivesolid by-product. The plasma effluents of the second stage are formedfrom a remote plasma of a fluorine-containing precursor.

In order to better understand and appreciate the invention, reference isnow made to FIG. 1 which is a flow chart of a silicon selective etchprocess according to disclosed embodiments. Silicon is an example of amaterial whose selectivity may be increased using the methods presentedherein. Prior to the first operation, a structure is formed in apatterned substrate. The structure possesses separate exposed regions ofsilicon oxide and silicon. The substrate is then delivered into aprocessing region (operation 110). Flows of ammonia and nitrogentrifluoride are initiated into a plasma region separate from thesubstrate processing region (operation 113). The separate plasma regionmay be referred to as a remote plasma region herein and may be adistinct module from the processing chamber or a compartment within theprocessing chamber. Remote plasma effluents (i.e. products from theremote plasma) are flowed into the processing region and allowed tointeract with the substrate surface (operation 115). Protective solidby-product is selectively formed over the exposed silicon oxide but notover the silicon (operation 118). The formation of the protective solidby-product consumes a top layer of the silicon oxide and the protectivesolid by-product possesses material from the plasma effluents andmaterial from the silicon oxide. Operations 113-118 are collectivelyreferred to herein as the first dry etch stage despite the fact thatvery little silicon oxide is consumed during the process (and even lessleaves the surface until operation 135).

Plasma effluents produced from nitrogen trifluoride and ammonia includea variety of molecules, molecular fragments and ionized species.Currently entertained theoretical mechanisms of the formation of theprotective solid by-product may or may not be entirely correct butplasma effluents are thought to include NH₄F and NH₄F.HF which reactreadily with low temperature exposed silicon-and-oxygen-containingregions described herein. Plasma effluents may react with a siliconoxide surface, for example, to form (NH₄)₂SiF₆, NH₃ and H₂O products.The NH₃ and H₂O are vapors under the processing conditions describedherein and may be removed from the substrate processing region by avacuum pump. A thin layer of (NH₄)₂SiF₆ solid by-product is left behindon the silicon oxide portion of the patterned substrate surface. Thesilicon (Si) originates from the exposed silicon oxide and the nitrogen,hydrogen and fluorine, which form the remainder of the (NH₄)₂SiF₆,originate from the plasma effluents. A variety of ratios of nitrogentrifluoride to ammonia into the remote plasma region may be used,however, between 1:1 and 4:1 or about a 2:1 ratio of ammonia to nitrogentrifluoride may be used in embodiments of the invention.

In general, the hydrogen-containing precursor flowed during the firstdry etch stage comprises at least one precursor selected from the groupconsisting of atomic hydrogen, molecular hydrogen, ammonia, aperhydrocarbon and an incompletely halogen-substituted hydrocarbon.Atomic hydrogen and molecular hydrogen are suitable for protectingsilicon-and-oxygen-containing material while etching silicon in the formof single crystalline silicon and polysilicon, however, their use shouldbe avoided when etching silicon-and-nitrogen-containing material such assilicon nitride. Atomic hydrogen and molecular hydrogen have been foundto grow protective solid by-product on silicon-and-nitrogen-containingmaterial in a manner similar to silicon-and-nitrogen-containingmaterial. The remaining sources of hydrogen may be used to selectivelyetch either silicon or silicon-and-nitrogen-containing material.

The inventors have found that the (protective) solid by-product is aneffective barrier against the following dry etch stage. A flow ofnitrogen trifluoride is then introduced into the remote plasma region(operation 120). During this stage, little or no hydrogen isco-introduced into the remote plasma region in embodiments of theinvention. This second fluorine-containing precursor may not be mixedwith a source of hydrogen and the second plasma effluents may then beessentially devoid of hydrogen. A small amount of ammonia or hydrogen(e.g. less than 1:5 or 1:10 H:F atomic flow ratio) may be added withoutundermining the highly selective etch rate of the exposed siliconregions. Other sources of fluorine may be used to augment or replace thenitrogen trifluoride. In general, a fluorine-containing precursor may beflowed into the plasma region and the fluorine-containing precursorcomprises at least one precursor selected from the group consisting ofatomic fluorine, diatomic fluorine, bromine trifluoride, chlorinetrifluoride, nitrogen trifluoride, hydrogen fluoride, sulfurhexafluoride and xenon difluoride. Even carbon containing precursors,such as carbon tetrafluoride, trifluoromethane, difluoromethane,fluoromethane and the like, can be added to the group already listed.

The plasma effluents formed in the remote plasma region are then flowedinto the substrate processing region (operation 125). The patternedsubstrate is selectively etched (operation 130) such that exposedsilicon is removed at a rate significantly greater than the etch rate ofsilicon oxide, in part, due to the coverage of the protective solidby-product. Operations 120-130 are collectively referred to herein asthe second dry etch stage. The etch selectivity may be greater than orabout 20:1, greater than or about 30:1, greater than or about 50:1 orgreater than or about 80:1 in disclosed embodiments. These etchselectivity ranges apply not only to (silicon):(silicon oxide) but tothe more general (silicon):(silicon-and-oxygen-containing material). Thereactive chemical species are removed from the substrate processingregion by heating the patterned substrate (operation 135). The substrateis then removed from the processing region (operation 145).

In general, just as with the first dry etch stage, thefluorine-containing precursor may comprise at least one precursorselected from the group consisting of atomic fluorine, diatomicfluorine, bromine trifluoride, chlorine trifluoride, nitrogentrifluoride, hydrogen fluoride, sulfur hexafluoride and xenondifluoride, carbon tetrafluoride, trifluoromethane, difluoromethane,fluoromethane and the like. The use of carbon-containing precursorgenerally may benefit from a concurrent flow of an oxygen-containingprecursor, during the second dry etch stage, to react with the carbonbefore it can be incorporated into the substrate.

The remote plasma etch processes presented herein have also been foundto aid the selective etch of silicon-and-nitrogen-containing material(e.g. silicon nitride) relative to silicon oxide orsilicon-and-oxygen-containing material in general. Previous dry-etcheshad achieved selectivity of (silicon nitride):(silicon oxide) as high asabout 2:1. Using the methods presented herein, the dry-etch selectivityfor (e.g. silicon-and-nitrogen-containingmaterial):(silicon-and-oxygen-containing material) may be greater thanor about 5:1, 10:1, 20:1, 50:1 or 100:1 in embodiments of the invention.Any measurement of the selectivities reported herein regarding bothsilicon and silicon-and-nitrogen-containing material is basicallylimited by the amount of higher etch rate material to be removed. Themore rapidly etched material (e.g. silicon andsilicon-and-nitrogen-containing material) may be essentially devoid ofoxygen in embodiments.

The temperature of the patterned substrate during the first dry etchstage may be below one of 60° C., 50° C., 40° C. or 35° C. inembodiments of the invention. The protective solid by-product formedduring the first dry etch stage remains on the patterned substrateduring the second dry etch stage and is removed during the subsequentsublimation step. The temperature of the substrate during the second dryetch stage may be between about −30° C. and about 80° C., in general, toensure that the protective solid by-product is not removed prematurely.Beneficially, the etch rate has been found to be higher for the lowertemperatures within this range. In embodiments, the temperature of thesubstrate during the second dry etch stage may be about −20° C. or more,0° C. or more, about 5° C. or more or about 10° C. or more. Thesubstrate temperature during the second dry etch stage may also be lessthan or about 75° C., less than or about 50° C., less than or about 30°C., less than or about 20° C., less than or about 15° C. or less than orabout 10° C. in disclosed embodiments. The temperature of the solidby-product and the patterned substrate may be raised above one of 90°C., 100° C., 120° C. or 140° C. during the full sublimation inembodiments of the invention.

The first dry-etch stage may last longer than or about 3 seconds, 5seconds or 10 seconds. The first dry-etch stage may last less than orabout 30 seconds, 20 seconds or 10 seconds in embodiments of theinvention. The second dry-etch stage may last greater than or about 15seconds or about 30 seconds, in embodiments. The second dry-etch stagemay last less than or about 2 minutes or about 1 minute in embodimentsof the invention. Any of the upper limits may be combined with any ofthe lower limits to provide additional ranges present in additionaldisclosed embodiments. The duration of the sublimation may be above oneof 45 seconds, 60 seconds, 75 seconds, 90 seconds or 120 seconds indisclosed embodiments.

During the first dry etch stage, the fluorine-containing precursorand/or the hydrogen-containing precursor may further include one or morerelatively inert gases such as He, N₂, Ar, or the like. The inert gascan be used to improve plasma stability. In an embodiment, thefluorine-containing gas includes NF₃ at a flow rate of between about 5sccm (standard cubic centimeters per minute) and 300 sccm, NH₃ at a flowrate of between about 10 sccm and 5 slm (standard liters per minute), Heat a flow rate of between about 0 sccm and 5 slm, and Ar at a flow rateof between about 0 sccm and 5 slm. Only a fluorine-containing precursoris required during the second dry etch stage. The fluorine-containingprecursor may further include one or more relatively inert gases such asHe, N₂, Ar, or the like. The inert gas can be used to improve plasmastability. In an embodiment, the fluorine-containing gas includes NF₃ ata flow rate of between about 5 sccm (standard cubic centimeters perminute) and 300 sccm, He at a flow rate of between about 0 sccm and 3slm (standard liters per minute), and Ar at a flow rate of between about0 sccm and 3 slm. Little or essentially no NH₃ (or otherhydrogen-containing precursor) is flowed during the second dry etchstage in embodiments of the invention. To be sure, somehydrogen-containing precursors may utilized during the second dry etchstage. The hydrogen-containing precursors may be combined with the otherprecursors or flowed separately into the plasma region, however, theconcentration should be kept low. Hydrogen may interact with thefluorine-containing precursor in the plasma to form precursors whichremove additional silicon oxide by forming solid by-product by-productson the oxide surface. This reaction reduces the selectivity of theexposed silicon, silicon nitride or silicon-and-nitrogen-containingregions as compared with exposed silicon oxide regions. Though somehydrogen may be useful to introduce in some embodiments, there may alsobe no or essentially no flow of hydrogen into the plasma region duringthe etch process in other embodiments. One of ordinary skill in the artwould recognize that other gases and/or flows may be used depending on anumber of factors including processing chamber configuration, substratesize, geometry and layout of features being etched, and the like.

During the first dry etch stage, the method includes applying energy tothe fluorine-containing precursor and the hydrogen-containing precursorwhile they are in the remote plasma region to generate the plasmaeffluents. During the second dry etch stage, the method includesapplying energy to the fluorine-containing precursor while it is in theremote plasma region to generate the plasma effluents. As would beappreciated by one of ordinary skill in the art, the plasmas duringeither stage may include a number of charged and neutral speciesincluding radicals and ions. The plasma may be generated using knowntechniques (e.g., RF, capacitively coupled, inductively coupled, and thelike). In an embodiment, the energy is applied using acapacitively-coupled plasma unit at a source power of between about 10 Wand 15000 W and a pressure of between about 0.2 Torr and 30 Torr. Thecapacitively-coupled plasma unit may be disposed remote from a gasreaction region of the processing chamber. For example, thecapacitively-coupled plasma unit and the plasma generation region may beseparated from the gas reaction region by a showerhead and/or an ionsuppressor.

The pressure within the substrate processing region during the first dryetch stage and/or second dry etch stage is below or about 50 Torr, belowor about 30 Torr, below or about 20 Torr, below or about 10 Torr orbelow or about 5 Torr. The pressure during the stages may be above orabout 0.1 Torr, above or about 0.2 Torr, above or about 0.5 Torr orabove or about 1 Torr in embodiments of the invention. Any of the upperlimits on temperature or pressure may be combined with lower limits toform additional embodiments. The pressure during the first dry etchstage may be higher than during the second dry etch stage because of thereliance on precursor combinations to form the precursors which createthe protective solid by-product.

Generally speaking, the processes described herein may be used tosuppress the dry-etch rate of films which contain silicon and oxygen(and not just silicon oxide). The remote plasma etch processes mayprotect silicon-and-oxygen-containing material which includes an atomicconcentration of about 30% or more silicon and about 30% or more oxygenin embodiments of the invention. The silicon-and-oxygen-containingmaterial may also consist essentially of silicon and oxygen, allowingfor small dopant concentrations and other undesirable or desirableminority additives. Of course, the silicon-and-oxygen-containingmaterial may be silicon oxide in embodiments of the invention.

As described, the remote plasma etch processes may etchsilicon-and-nitrogen-containing material faster thansilicon-and-oxygen-containing material. Thesilicon-and-nitrogen-containing material may include an atomicconcentration of about 30% or more silicon and about 30% or morenitrogen in embodiments of the invention. Thesilicon-and-nitrogen-containing material may also consist essentially ofsilicon and nitrogen, allowing for small concentrations of undesirableor desirable minority additives. Of course, thesilicon-and-nitrogen-containing material may be silicon nitride inembodiments of the invention.

Additional process parameters are disclosed in the course of describingan exemplary processing chamber and system.

Exemplary Processing System

Processing chambers that may implement embodiments of the presentinvention may be included within processing platforms such as theCENTURA® and PRODUCER® systems, available from Applied Materials, Inc.of Santa Clara, Calif. Examples of substrate processing chambers thatcan be used with exemplary methods of the invention may include thoseshown and described in co-assigned U.S. Provisional Patent App. No.60/803,499 to Lubomirsky et al, filed May 30, 2006, and titled “PROCESSCHAMBER FOR DIELECTRIC GAPFILL,” the entire contents of which is hereinincorporated by reference for all purposes. Additional exemplary systemsmay include those shown and described in U.S. Pat. Nos. 6,387,207 and6,830,624, which are also incorporated herein by reference for allpurposes.

FIG. 2A is a substrate processing chamber 200 according to disclosedembodiments. A remote plasma system 210 may process thefluorine-containing precursor which then travels through a gas inletassembly 211. Two distinct gas supply channels are visible within thegas inlet assembly 211. A first channel 212 carries a gas that passesthrough the remote plasma system 210 (RPS), while a second channel 213bypasses the remote plasma system 210. Either channel may be used forthe fluorine-containing precursor, in embodiments. On the other hand,the first channel 212 may be used for the process gas and the secondchannel 213 may be used for a treatment gas. The lid (or conductive topportion) 221 and a perforated partition or showerhead 253 are shown withan insulating ring 224 in between, which allows an AC potential to beapplied to the lid 221 relative to showerhead 253. The AC potentialstrikes a plasma in chamber plasma region 220. The process gas maytravel through first channel 212 into chamber plasma region 220 and maybe excited by a plasma in chamber plasma region 220 alone or incombination with remote plasma system 210. If the process gas (thefluorine-containing precursor) flows through second channel 213, thenonly the chamber plasma region 220 is used for excitation. Thecombination of chamber plasma region 220 and/or remote plasma system 210may be referred to as a remote plasma system herein. The perforatedpartition (also referred to as a showerhead) 253 separates chamberplasma region 220 from a substrate processing region 270 beneathshowerhead 253. Showerhead 253 allows a plasma present in chamber plasmaregion 220 to avoid directly exciting gases in substrate processingregion 270, while still allowing excited species to travel from chamberplasma region 220 into substrate processing region 270.

Showerhead 253 is positioned between chamber plasma region 220 andsubstrate processing region 270 and allows plasma effluents (excitedderivatives of precursors or other gases) created within remote plasmasystem 210 and/or chamber plasma region 220 to pass through a pluralityof through-holes 256 that traverse the thickness of the plate. Theshowerhead 253 also has one or more hollow volumes 251 which can befilled with a precursor in the form of a vapor or gas and pass throughsmall holes 255 into substrate processing region 270 but not directlyinto chamber plasma region 220. Showerhead 253 is thicker than thelength of the smallest diameter 250 of the through-holes 256 in thisdisclosed embodiment. In order to maintain a significant concentrationof excited species penetrating from chamber plasma region 220 tosubstrate processing region 270, the length 226 of the smallest diameter250 of the through-holes may be restricted by forming larger diameterportions of through-holes 256 part way through the showerhead 253. Thelength of the smallest diameter 250 of the through-holes 256 may be thesame order of magnitude as the smallest diameter of the through-holes256 or less in disclosed embodiments.

An ion suppressor may be used to control the ion density which passesinto the substrate processing region. This may serve to further increasethe etch rate difference between the protectedsilicon-and-oxygen-containing material and the silicon orsilicon-and-nitrogen-containing material. The ion suppression elementfunctions to reduce or eliminate ionically charged species travelingfrom the plasma generation region to the substrate. Uncharged neutraland radical species may pass through the openings in the ion suppressorto react at the substrate. It should be noted that complete eliminationof ionically charged species in the reaction region surrounding thesubstrate is not always the desired goal. In many instances, ionicspecies are required to reach the substrate in order to perform the etchand/or deposition process. In these instances, the ion suppressor helpscontrol the concentration of ionic species in the reaction region at alevel that assists the process.

In accordance with some embodiments of the invention, an ion suppressoras described herein may be used to provide radical and/or neutralspecies for selectively etching substrates. In one embodiment, forexample, an ion suppressor is used to provide fluorine containing plasmaeffluents to more selectively etch silicon or silicon nitride. Using theionically filtered plasma effluents in addition to the protective solidby-product, the etch rate selectivity of, e.g., silicon relative tosilicon oxide may be further increased to the values described herein.The ion suppressor may be used to provide a reactive gas having a higherconcentration of radicals than ions. Because most of the chargedparticles of a plasma are filtered or removed by the ion suppressor, thesubstrate may not necessarily be biased during the etch process. Such aprocess using radicals and other neutral species can reduce plasmadamage compared to conventional plasma etch processes that includesputtering and bombardment.

Showerhead 253 may be configured to serve the purpose of the ionsuppressor as shown in FIG. 2A. Alternatively, a separate processingchamber element may be included (not shown) which suppresses the ionconcentration traveling into substrate processing region 270. Lid 221and showerhead 253 may function as a first electrode and secondelectrode, respectively, so that lid 221 and showerhead 253 may receivedifferent electric voltages. In these configurations, electrical power(e.g., RF power) may be applied to lid 221, showerhead 253, or both. Forexample, electrical power may be applied to lid 221 while showerhead 253(serving as ion suppressor) is grounded. The substrate processing systemmay include a RF generator that provides electrical power to the lidand/or showerhead 253. The voltage applied to lid 221 may facilitate auniform distribution of plasma (i.e., reduce localized plasma) withinchamber plasma region 220. To enable the formation of a plasma inchamber plasma region 220, insulating ring 224 may electrically insulatelid 221 from showerhead 253. Insulating ring 224 may be made from aceramic and may have a high breakdown voltage to avoid sparking.Portions of substrate processing chamber 200 near thecapacitively-coupled plasma components just described may furtherinclude a cooling unit (not shown) that includes one or more coolingfluid channels to cool surfaces exposed to the plasma with a circulatingcoolant (e.g., water).

In the embodiment shown, showerhead 253 may distribute (viathrough-holes 256) process gases which contain oxygen, fluorine and/ornitrogen and/or plasma effluents of such process gases upon excitationby a plasma in chamber plasma region 220. In embodiments, the processgas introduced into the remote plasma system 210 and/or chamber plasmaregion 220 may contain fluorine (e.g. F₂, NF₃ or XeF₂). The process gasmay also include a carrier gas such as helium, argon, nitrogen (N₂),etc. Plasma effluents may include ionized or neutral derivatives of theprocess gas and may also be referred to herein as radical-fluorinereferring to the atomic constituent of the process gas introduced.

Through-holes 256 are configured to suppress the migration ofionically-charged species out of the chamber plasma region 220 whileallowing uncharged neutral or radical species to pass through showerhead253 into substrate processing region 270. These uncharged species mayinclude highly reactive species that are transported with less-reactivecarrier gas by through-holes 256. As noted above, the migration of ionicspecies by through-holes 256 may be reduced, and in some instancescompletely suppressed. Controlling the amount of ionic species passingthrough showerhead 253 provides increased control over the gas mixturebrought into contact with the underlying wafer substrate, which in turnincreases control of the deposition and/or etch characteristics of thegas mixture. For example, adjustments in the ion concentration of thegas mixture can significantly alter its etch selectivity (e.g., siliconnitride:silicon oxide etch ratios).

In embodiments, the number of through-holes 256 may be between about 60and about 2000. Through-holes 256 may have a variety of shapes but aremost easily made round. The smallest diameter 250 of through-holes 256may be between about 0.5 mm and about 20 mm or between about 1 mm andabout 6 mm in disclosed embodiments. There is also latitude in choosingthe cross-sectional shape of through-holes, which may be made conical,cylindrical or combinations of the two shapes. The number of small holes255 used to introduce unexcited precursors into substrate processingregion 270 may be between about 100 and about 5000 or between about 500and about 2000 in disclosed embodiments. The diameter of the small holes255 may be between about 0.1 mm and about 2 mm.

Through-holes 256 may be configured to control the passage of theplasma-activated gas (i.e., the ionic, radical, and/or neutral species)through showerhead 253. For example, the aspect ratio of the holes(i.e., the hole diameter to length) and/or the geometry of the holes maybe controlled so that the flow of ionically-charged species in theactivated gas passing through showerhead 253 is reduced. Through-holes256 in showerhead 253 may include a tapered portion that faces chamberplasma region 220, and a cylindrical portion that faces substrateprocessing region 270. The cylindrical portion may be proportioned anddimensioned to control the flow of ionic species passing into substrateprocessing region 270. An adjustable electrical bias may also be appliedto showerhead 253 as an additional means to control the flow of ionicspecies through showerhead 253.

Alternatively, through-holes 256 may have a smaller inner diameter (ID)toward the top surface of showerhead 253 and a larger ID toward thebottom surface. In addition, the bottom edge of through-holes 256 may bechamfered to help evenly distribute the plasma effluents in substrateprocessing region 270 as the plasma effluents exit the showerhead andthereby promote even distribution of the plasma effluents and precursorgases. The smaller ID may be placed at a variety of locations alongthrough-holes 256 and still allow showerhead 253 to reduce the iondensity within substrate processing region 270. The reduction in iondensity results from an increase in the number of collisions with wallsprior to entry into substrate processing region 270. Each collisionincreases the probability that an ion is neutralized by the acquisitionor loss of an electron from the wall. Generally speaking, the smaller IDof through-holes 256 may be between about 0.2 mm and about 20 mm. Inother embodiments, the smaller ID may be between about 1 mm and 6 mm orbetween about 0.2 mm and about 5 mm. Further, aspect ratios of thethrough-holes 256 (i.e., the smaller ID to hole length) may beapproximately 1 to 20. The smaller ID of the through-holes may be theminimum ID found along the length of the through-holes. The crosssectional shape of through-holes 256 may be generally cylindrical,conical, or any combination thereof.

FIG. 2B is a bottom view of a showerhead 253 for use with a processingchamber according to disclosed embodiments. Showerhead 253 correspondswith the showerhead shown in FIG. 2A. Through-holes 256 are depictedwith a larger inner-diameter (ID) on the bottom of showerhead 253 and asmaller ID at the top. Small holes 255 are distributed substantiallyevenly over the surface of the showerhead, even amongst thethrough-holes 256 which helps to provide more even mixing than otherembodiments described herein.

An exemplary patterned substrate may be supported by a pedestal (notshown) within substrate processing region 270 when fluorine-containingplasma effluents and oxygen-containing plasma effluents arrive throughthrough-holes 256 in showerhead 253. Though substrate processing region270 may be equipped to support a plasma for other processes such ascuring, no plasma is present during the etching of patterned substrate,in embodiments of the invention.

A plasma may be ignited either in chamber plasma region 220 aboveshowerhead 253 or substrate processing region 270 below showerhead 253.A plasma is present in chamber plasma region 220 to produce theradical-fluorine from an inflow of the fluorine-containing precursor. AnAC voltage typically in the radio frequency (RF) range is appliedbetween the conductive top portion (lid 221) of the processing chamberand showerhead 253 to ignite a plasma in chamber plasma region 220during deposition. An RF power supply generates a high RF frequency of13.56 MHz but may also generate other frequencies alone or incombination with the 13.56 MHz frequency.

The top plasma may be left at low or no power when the bottom plasma inthe substrate processing region 270 is turned on to either cure a filmor clean the interior surfaces bordering substrate processing region270. A plasma in substrate processing region 270 is ignited by applyingan AC voltage between showerhead 253 and the pedestal or bottom of thechamber. A cleaning gas may be introduced into substrate processingregion 270 while the plasma is present.

The pedestal may have a heat exchange channel through which a heatexchange fluid flows to control the temperature of the substrate. Thisconfiguration allows the substrate temperature to be cooled or heated tomaintain relatively low temperatures (from room temperature throughabout 120° C.). The heat exchange fluid may comprise ethylene glycol andwater. The wafer support platter of the pedestal (preferably aluminum,ceramic, or a combination thereof) may also be resistively heated inorder to achieve relatively high temperatures (from about 120° C.through about 1100° C.) using an embedded single-loop embedded heaterelement configured to make two full turns in the form of parallelconcentric circles. An outer portion of the heater element may runadjacent to a perimeter of the support platter, while an inner portionruns on the path of a concentric circle having a smaller radius. Thewiring to the heater element passes through the stem of the pedestal.

The chamber plasma region or a region in a remote plasma system may bereferred to as a remote plasma region. In embodiments, the radicalprecursor (i.e. radical-fluorine) is formed in the remote plasma regionand travels into the substrate processing region where the silicon orsilicon-and-nitrogen-containing material is preferentially etched.Plasma power may essentially be applied only to the remote plasmaregion, in embodiments, to ensure that the radical-fluorine and theradical-oxygen (which together may be referred to as plasma effluents)are not further excited in the substrate processing region.

In embodiments employing a chamber plasma region, the excited plasmaeffluents are generated in a section of the substrate processing regionpartitioned from a deposition region. The deposition region, also knownherein as the substrate processing region, is where the plasma effluentsmix and react to etch the patterned substrate (e.g., a semiconductorwafer). The excited plasma effluents may also be accompanied by inertgases (in the exemplary case, argon). The substrate processing regionmay be described herein as “plasma-free” during the etches of thepatterned substrate. “Plasma-free” does not necessarily mean the regionis devoid of plasma. A relatively low concentration of ionized speciesand free electrons created within the plasma region do travel throughpores (apertures) in the partition (showerhead/ion suppressor) due tothe shapes and sizes of through-holes 256. In some embodiments, there isessentially no concentration of ionized species and free electronswithin the substrate processing region during the first or second etchstages. The borders of the plasma in the chamber plasma region are hardto define and may encroach upon the substrate processing region throughthe apertures in the showerhead. In the case of an inductively-coupledplasma, a small amount of ionization may be effected within thesubstrate processing region directly. Furthermore, a low intensityplasma may be created in the substrate processing region withouteliminating desirable features of the forming film. All causes for aplasma having much lower intensity ion density than the chamber plasmaregion (or a remote plasma region, for that matter) during the creationof the excited plasma effluents do not deviate from the scope of“plasma-free” as used herein.

Nitrogen trifluoride (or another fluorine-containing precursor) may beflowed into chamber plasma region 220 at rates between about 25 sccm andabout 200 sccm, between about 50 sccm and about 150 sccm or betweenabout 75 sccm and about 125 sccm in disclosed embodiments. Oxygen (O₂)may be flowed into chamber plasma region 220 at rates greater than orabout 250 sccm, greater than or about 500 sccm or greater than or about1 slm in disclosed embodiments.

Combined flow rates of fluorine-containing precursor andoxygen-containing precursor into the chamber may account for 0.05% toabout 20% by volume of the overall gas mixture; the remainder beingcarrier gases. The fluorine-containing precursor and theoxygen-containing precursor are flowed into the remote plasma region butthe plasma effluents have the same volumetric flow ratio, inembodiments. In the case of the fluorine-containing precursor, a purgeor carrier gas may be first initiated into the remote plasma regionbefore those of the fluorine-containing gas to stabilize the pressurewithin the remote plasma region.

Plasma power applied to the remote plasma region can be a variety offrequencies or a combination of multiple frequencies. In the exemplaryprocessing system the plasma is provided by RF power delivered betweenlid 221 and showerhead 253. The RF power may be between about 10 Wattsand about 15000 Watts, between about 20 Watts and about 1500 Watts orbetween about 50 Watts and about 500 Watts in disclosed embodiments. TheRF frequency applied in the exemplary processing system may be low RFfrequencies less than about 200 kHz, high RF frequencies between about10 MHz and about 15 MHz or microwave frequencies greater than or about 1GHz in disclosed embodiments.

Substrate processing region 270 can be maintained at a variety ofpressures during the flow of carrier gases and plasma effluents intosubstrate processing region 270. The pressure within the substrateprocessing region is below or about 50 Torr, below or about 30 Torr,below or about 20 Torr, below or about 10 Torr or below or about 5 Torr.The pressure may be above or about 0.1 Torr, above or about 0.2 Torr,above or about 0.5 Torr or above or about 1 Torr in embodiments of theinvention. Lower limits on the pressure may be combined with upperlimits on the pressure to arrive at further embodiments of theinvention.

In one or more embodiments, the substrate processing chamber 200 can beintegrated into a variety of multi-processing platforms, including theProducer™ GT, Centura™ AP and Endura™ platforms available from AppliedMaterials, Inc. located in Santa Clara, Calif. Such a processingplatform is capable of performing several processing operations withoutbreaking vacuum. Processing chambers that may implement embodiments ofthe present invention may include dielectric etch chambers or a varietyof chemical vapor deposition chambers, among other types of chambers.

Embodiments of the deposition systems may be incorporated into largerfabrication systems for producing integrated circuit chips. FIG. 3 showsone such system 300 of deposition, baking and curing chambers accordingto disclosed embodiments. In the figure, a pair of FOUPs (front openingunified pods) 302 supply substrate substrates (e.g., 300 mm diameterwafers) that are received by robotic arms 304 and placed into a lowpressure holding areas 306 before being placed into one of the waferprocessing chambers 308 a-f. A second robotic arm 310 may be used totransport the substrate wafers from the low pressure holding areas 306to the wafer processing chambers 308 a-f and back. Each of waferprocessing chambers 308 a-f, can be outfitted to perform a number ofsubstrate processing operations including the dry etch processesdescribed herein in addition to cyclical layer deposition (CLD), atomiclayer deposition (ALD), chemical vapor deposition (CVD), physical vapordeposition (PVD), etch, pre-clean, degas, orientation and othersubstrate processes.

The wafer processing chambers 308 a-f may include one or more systemcomponents for depositing, annealing, curing and/or etching a flowabledielectric film on the substrate wafer. In one configuration, two pairsof the processing chamber (e.g., 308 c-d and 308 e-f) may be used todeposit dielectric material on the substrate, and the third pair ofprocessing chambers (e.g., 308 a-b) may be used to etch the depositeddielectric. In another configuration, all three pairs of chambers (e.g.,308 a-f) may be configured to etch a dielectric film on the substrate.Any one or more of the processes described may be carried out onchamber(s) separated from the fabrication system shown in disclosedembodiments.

The substrate processing system is controlled by a system controller. Inan exemplary embodiment, the system controller includes a hard diskdrive, a floppy disk drive and a processor. The processor contains asingle-board computer (SBC), analog and digital input/output boards,interface boards and stepper motor controller boards. Various parts ofCVD system conform to the Versa Modular European (VME) standard whichdefines board, card cage, and connector dimensions and types. The VMEstandard also defines the bus structure as having a 16-bit data bus anda 24-bit address bus.

System controller 357 is used to control motors, valves, flowcontrollers, power supplies and other functions required to carry outprocess recipes described herein. A gas handling system 355 may also becontrolled by system controller 357 to introduce gases to one or all ofthe wafer processing chambers 308 a-f. System controller 357 may rely onfeedback from optical sensors to determine and adjust the position ofmovable mechanical assemblies in gas handling system 355 and/or in waferprocessing chambers 308 a-f. Mechanical assemblies may include therobot, throttle valves and susceptors which are moved by motors underthe control of system controller 357.

In an exemplary embodiment, system controller 357 includes a hard diskdrive (memory), USB ports, a floppy disk drive and a processor. Systemcontroller 357 includes analog and digital input/output boards,interface boards and stepper motor controller boards.

Various parts of multi-chamber processing system 300 which containssubstrate processing chamber 200 are controlled by system controller357. The system controller executes system control software in the formof a computer program stored on computer-readable medium such as a harddisk, a floppy disk or a flash memory thumb drive. Other types of memorycan also be used. The computer program includes sets of instructionsthat dictate the timing, mixture of gases, chamber pressure, chambertemperature, RF power levels, susceptor position, and other parametersof a particular process.

A process for etching, depositing or otherwise processing a film on asubstrate or a process for cleaning chamber can be implemented using acomputer program product that is executed by the controller. Thecomputer program code can be written in any conventional computerreadable programming language: for example, 68000 assembly language, C,C++, Pascal, Fortran or others. Suitable program code is entered into asingle file, or multiple files, using a conventional text editor, andstored or embodied in a computer usable medium, such as a memory systemof the computer. If the entered code text is in a high level language,the code is compiled, and the resultant compiler code is then linkedwith an object code of precompiled Microsoft Windows® library routines.To execute the linked, compiled object code the system user invokes theobject code, causing the computer system to load the code in memory. TheCPU then reads and executes the code to perform the tasks identified inthe program.

The interface between a user and the controller may be via atouch-sensitive monitor and may also include a mouse and keyboard. Inone embodiment two monitors are used, one mounted in the clean room wallfor the operators and the other behind the wall for the servicetechnicians. The two monitors may simultaneously display the sameinformation, in which case only one is configured to accept input at atime. To select a particular screen or function, the operator touches adesignated area on the display screen with a finger or the mouse. Thetouched area changes its highlighted color, or a new menu or screen isdisplayed, confirming the operator's selection.

As used herein “substrate” may be a support substrate with or withoutlayers formed thereon. The patterned substrate may be an insulator or asemiconductor of a variety of doping concentrations and profiles andmay, for example, be a semiconductor substrate of the type used in themanufacture of integrated circuits. Exposed “silicon” of the patternedsubstrate is predominantly Si but may include minority concentrations ofother elemental constituents such as boron, phosphorus, nitrogen,oxygen, hydrogen, carbon and the like. The term “silicon” may representsingle crystalline silicon or polysilicon. Exposed “silicon nitride” ofthe patterned substrate is predominantly Si₃N₄ but may include minorityconcentrations of other elemental constituents such as oxygen, hydrogen,carbon and the like. Exposed “silicon oxide” of the patterned substrateis predominantly SiO₂ but may include concentrations of other elementalconstituents such as nitrogen, hydrogen, carbon and the like. In someembodiments, silicon oxide films etched using the methods disclosedherein consist essentially of silicon and oxygen. The term “precursor”is used to refer to any process gas which takes part in a reaction toeither remove material from or deposit material onto a surface. “Plasmaeffluents” describe gas exiting from the chamber plasma region andentering the substrate processing region. Plasma effluents are in an“excited state” wherein at least some of the gas molecules are invibrationally-excited, dissociated and/or ionized states. A “radicalprecursor” is used to describe plasma effluents (a gas in an excitedstate which is exiting a plasma) which participate in a reaction toeither remove material from or deposit material on a surface.“Radical-fluorine” (or “radical-oxygen”) are radical precursors whichcontain fluorine (or oxygen) but may contain other elementalconstituents. The phrase “inert gas” refers to any gas which does notform chemical bonds when etching or being incorporated into a film.Exemplary inert gases include noble gases but may include other gases solong as no chemical bonds are formed when (typically) trace amounts aretrapped in a film.

The terms “gap” and “trench” are used throughout with no implicationthat the etched geometry has a large horizontal aspect ratio. Viewedfrom above the surface, trenches may appear circular, oval, polygonal,rectangular, or a variety of other shapes. A trench may be in the shapeof a moat around an island of material. The term “via” is used to referto a low aspect ratio trench (as viewed from above) which may or may notbe filled with metal to form a vertical electrical connection. As usedherein, a conformal etch process refers to a generally uniform removalof material on a surface in the same shape as the surface, i.e., thesurface of the etched layer and the pre-etch surface are generallyparallel. A person having ordinary skill in the art will recognize thatthe etched interface likely cannot be 100% conformal and thus the term“generally” allows for acceptable tolerances.

Having disclosed several embodiments, it will be recognized by those ofskill in the art that various modifications, alternative constructions,and equivalents may be used without departing from the spirit of thedisclosed embodiments. Additionally, a number of well known processesand elements have not been described in order to avoid unnecessarilyobscuring the present invention. Accordingly, the above descriptionshould not be taken as limiting the scope of the invention.

Where a range of values is provided, it is understood that eachintervening value, to the tenth of the unit of the lower limit unlessthe context clearly dictates otherwise, between the upper and lowerlimits of that range is also specifically disclosed. Each smaller rangebetween any stated value or intervening value in a stated range and anyother stated or intervening value in that stated range is encompassed.The upper and lower limits of these smaller ranges may independently beincluded or excluded in the range, and each range where either, neitheror both limits are included in the smaller ranges is also encompassedwithin the invention, subject to any specifically excluded limit in thestated range. Where the stated range includes one or both of the limits,ranges excluding either or both of those included limits are alsoincluded.

As used herein and in the appended claims, the singular forms “a”, “an”,and “the” include plural referents unless the context clearly dictatesotherwise. Thus, for example, reference to “a process” includes aplurality of such processes and reference to “the dielectric material”includes reference to one or more dielectric materials and equivalentsthereof known to those skilled in the art, and so forth.

Also, the words “comprise,” “comprising,” “include,” “including,” and“includes” when used in this specification and in the following claimsare intended to specify the presence of stated features, integers,components, or steps, but they do not preclude the presence or additionof one or more other features, integers, components, steps, acts, orgroups.

1. A method of etching a patterned substrate in a substrate processingregion of a substrate processing chamber, wherein the patternedsubstrate has an exposed silicon-and-oxygen-containing region and anexposed region of a second material having a different chemicalstoichiometry from the exposed silicon-and-oxygen-containing region, themethod of etching the patterned substrate comprising sequential stepsof: (1) a first dry etch stage comprising: flowing each of a firstfluorine-containing precursor and a hydrogen-containing precursor into aremote plasma region fluidly coupled to the substrate processing regionwhile forming a first plasma in the remote plasma region to producefirst plasma effluents, and forming protective solid by-product on theexposed silicon-and-oxygen-containing region to form a protectedsilicon-and-oxygen-containing region, wherein forming the protectivesolid by-product comprises flowing the first plasma effluents into thesubstrate processing region in a showerhead; (2) a second dry etch stagecomprising flowing a second fluorine-containing precursor into theremote plasma region while forming a second plasma in the remote plasmaregion to produce second plasma effluents, and etching the exposedregion of the second material faster than the protectedsilicon-and-oxygen-containing region by flowing the second plasmaeffluents into the substrate processing region through through-holes inthe showerhead; and (3) sublimating the protective solid by-product fromthe protected silicon-and-oxygen-containing region by raising atemperature of the patterned substrate.
 2. The method of etching thepatterned substrate of claim 1 wherein the exposedsilicon-and-oxygen-containing region is silicon oxide.
 3. The method ofetching the patterned substrate of claim 1 wherein the exposedsilicon-and-oxygen-containing region consists essentially of silicon andoxygen.
 4. The method of etching the patterned substrate of claim 1wherein the exposed silicon-and-oxygen-containing region comprises about30% or more silicon and about 30% or more oxygen.
 5. The method ofetching the patterned substrate of claim 1 wherein the temperature ofthe patterned substrate is greater than or about −20° C. and less thanor about 75° C. during each of the first dry etch stage and the seconddry etch stage.
 6. The method of etching the patterned substrate ofclaim 1 wherein a pressure within the substrate processing region isbelow or about 50 Torr and above or about 0.1 Torr during each of thefirst dry etch stage and the second dry etch stage.
 7. The method ofetching the patterned substrate of claim 1 wherein forming the firstplasma in the remote plasma region and the second plasma in the remoteplasma region comprises applying RF power between about 10 Watts andabout 15000 Watts to the remote plasma region during each of the firstdry etch stage and the second dry etch stage.
 8. The method of etchingthe patterned substrate of claim 1 wherein the first plasma and thesecond plasma are both capacitively-coupled plasmas.
 9. The method ofetching the patterned substrate of claim 1 wherein the second materialis single crystalline silicon or polysilicon.
 10. The method of etchingthe patterned substrate of claim 9 wherein an etch selectivity of themethod of etching the patterned substrate (exposed region of the secondmaterial: exposed silicon-and-oxygen-containing region) is greater thanor about 20:1.
 11. The method of etching the patterned substrate ofclaim 1 wherein the second material comprises silicon and nitrogen. 12.The method of etching the patterned substrate of claim 11 wherein anetch selectivity of the method of etching the patterned substrate(exposed region of the second material: exposedsilicon-and-oxygen-containing region) is greater than or about 5:1. 13.The method of etching the patterned substrate of claim 1 wherein thesecond material comprises an atomic percentage of about 30% or moresilicon and about 30% or more nitrogen.
 14. The method of etching thepatterned substrate of claim 1 wherein the second material is siliconnitride.
 15. The method of etching the patterned substrate of claim 1wherein the substrate processing region is essentially plasma-freeduring each of the first dry etch stage and the second dry etch stage.16. The method of etching the patterned substrate of claim 1 wherein thefirst fluorine-containing precursor comprises at least one of atomicfluorine, diatomic fluorine, nitrogen trifluoride, carbon tetrafluorideand xenon difluoride.
 17. The method of etching the patterned substrateof claim 1 wherein the hydrogen-containing precursor comprises at leastone of atomic hydrogen, molecular hydrogen, ammonia, a perhydrocarbonand an incompletely halogen-substituted hydrocarbon.
 18. The method ofetching the patterned substrate of claim 1 wherein the secondfluorine-containing precursor is not mixed with a source of hydrogen andthe second plasma effluents is essentially devoid of hydrogen.
 19. Themethod of etching the patterned substrate of claim 1 wherein there isessentially no concentration of ionized species and free electronswithin the substrate processing region during the second dry etch stage.20. The method of etching the patterned substrate of claim 1 wherein thesecond material is essentially devoid of oxygen.